Title: Photostability Can Be Significantly Modulated by Molecular Packing in Glasses

Abstract

While previous work has demonstrated that molecular packing in organic crystals can strongly influence photochemical stability, efforts to tune photostability in amorphous materials have shown much smaller effects. Here we show that physical vapor deposition can substantially improve the photostability of organic glasses. Disperse Orange 37 (DO37), an azobenzene derivative, is studied as a model system. Photostability is assessed through changes in the density and molecular orientation of glassy thin films during light irradiation. By optimizing the substrate temperature used for deposition, we can increase photostability by a factor of 50 relative to the liquid-cooled glass. Photostability correlates with glass density, with density increases of up to 1.3%. Coarse-grained molecular simulations, which mimic glass preparation and the photoisomerization reaction, also indicate that glasses with higher density have substantially increased photostability. These results provide insights that may assist in the design of organic photovoltaics and light emission devices with longer lifetimes.

@article{osti_1411404,
title = {Photostability Can Be Significantly Modulated by Molecular Packing in Glasses},
author = {Qiu, Yue and Antony, Lucas W. and de Pablo, Juan J. and Ediger, M. D.},
abstractNote = {While previous work has demonstrated that molecular packing in organic crystals can strongly influence photochemical stability, efforts to tune photostability in amorphous materials have shown much smaller effects. Here we show that physical vapor deposition can substantially improve the photostability of organic glasses. Disperse Orange 37 (DO37), an azobenzene derivative, is studied as a model system. Photostability is assessed through changes in the density and molecular orientation of glassy thin films during light irradiation. By optimizing the substrate temperature used for deposition, we can increase photostability by a factor of 50 relative to the liquid-cooled glass. Photostability correlates with glass density, with density increases of up to 1.3%. Coarse-grained molecular simulations, which mimic glass preparation and the photoisomerization reaction, also indicate that glasses with higher density have substantially increased photostability. These results provide insights that may assist in the design of organic photovoltaics and light emission devices with longer lifetimes.},
doi = {10.1021/jacs.6b06372},
journal = {Journal of the American Chemical Society},
number = 35,
volume = 138,
place = {United States},
year = {Fri Aug 12 00:00:00 EDT 2016},
month = {Fri Aug 12 00:00:00 EDT 2016}
}

While previous work has demonstrated that molecular packing in organic crystals can strongly influence photochemical stability, efforts to tune photostability in amorphous materials have shown much smaller effects. Here we show that physical vapor deposition can substantially improve the photostability of organic glasses. Disperse Orange 37 (DO37), an azobenzene derivative, is studied as a model system. Photostability is assessed through changes in the density and molecular orientation of glassy thin films during light irradiation. By optimizing the substrate temperature used for deposition, we can increase photostability by a factor of 50 relative to the liquid-cooled glass. Photostability correlates with glassmore » density, with density increases of up to 1.3%. Coarse-grained molecular simulations, which mimic glass preparation and the photoisomerization reaction, also indicate that glasses with higher density have substantially increased photostability. These results provide insights that may assist in the design of organic photovoltaics and light emission devices with longer lifetimes.« less

Using molecular dynamics simulations, we have studied the atomic correlations characterizing the second peak in the radial distribution function (RDF) of metallic glasses and liquids. The analysis was conducted from the perspective of different connection schemes of atomic packing motifs, based on the number of shared atoms between two linked coordination polyhedra. The results demonstrate that the cluster connections by face-sharing, specifically with three common atoms, are most favored when transitioning from the liquid to glassy state, and exhibit the stiffest elastic response during shear deformation. These properties of the connections and the resultant atomic correlations are generally the samemore » for different types of packing motifs in different alloys. Splitting of the second RDF peak was observed for the inherent structure of the equilibrium liquid, originating solely from cluster connections; this trait can then be inherited in the metallic glass formed via subsequent quenching of the parent liquid through the glass transition, in the absence of any additional type of local structural order. In conclusion, increasing ordering and cluster connection during cooling, however, may tune the position and intensity of the split peaks.« less

Glasses of a model smectic liquid crystal-forming molecule, itraconazole, were prepared by vapor deposition onto substrates with temperatures ranging from T substrate = 0.78T g to 1.02T g, where T g (=330 K) is the glass transition temperature. The films were characterized using X-ray scattering techniques. For T substrate near and below T g, glasses with layered smectic-like structures can be prepared and the layer spacing can be tuned by 16% through the choice of T substrate. Remarkably, glasses prepared with T substrate values above T g exhibit levels of structural organization much higher than that of a thermally annealedmore » film. These results are explained by a mechanism based upon a preferred molecular orientation and enhanced molecular motion at the free surface, indicating that molecular organization in the glass is independent of the anchoring preferred at the substrate. Furthermore, these results suggest new strategies for optimizing molecular packing within active layers of organic electronic and optoelectronic devices.« less

Using molecular dynamics simulations, we have studied the atomic correlations characterizing the second peak in the radial distribution function (RDF) of metallic glasses and liquids. The analysis was conducted from the perspective of different connection schemes of atomic packing motifs, based on the number of shared atoms between two linked coordination polyhedra. The results demonstrate that the cluster connections by face-sharing, specifically with three common atoms, are most favored when transitioning from the liquid to glassy state, and exhibit the stiffest elastic response during shear deformation. These properties of the connections and the resultant atomic correlations are generally the samemore » for different types of packing motifs in different alloys. Splitting of the second RDF peak was observed for the inherent structure of the equilibrium liquid, originating solely from cluster connections; this trait can then be inherited in the metallic glass formed via subsequent quenching of the parent liquid through the glass transition, in the absence of any additional type of local structural order. Increasing ordering and cluster connection during cooling, however, may tune the position and intensity of the split peaks.« less

Journal ArticleDing, Jun
; Asta, Mark
; Ritchie, Robert O. - Proceedings of the National Academy of Sciences of the United States of America

This work addresses the long-standing debate over fractal models of packing structure in metallic glasses (MGs). Through detailed fractal and percolation analyses of MG structures, derived from simulations spanning a range of compositions and quenching rates, we conclude that there is no fractal atomic-level structure associated with the packing of all atoms or solute-centered clusters. The results are in contradiction with conclusions derived from previous studies based on analyses of shifts in radial distribution function and structure factor peaks associated with volume changes induced by pressure and compositional variations. Here in this paper, the interpretation of such shifts is shownmore » to be challenged by the heterogeneous nature of MG structure and deformation at the atomic scale. Moreover, our analysis in the present work illustrates clearly the percolation theory applied to MGs, for example, the percolation threshold and characteristics of percolation clusters formed by subsets of atoms, which can have important consequences for structure–property relationships in these amorphous materials.« less